Morphological design strategies to tailor out-of-plane charge transport in conjugated polymer systems for device applications.

The transport of charge carriers throughout an active conjugated polymer (CP) host, characterized by a heterogeneous morphology of locally varying degrees of order and disorder, profoundly influences the performance of CP-based electronic devices, including diodes, photovoltaics, sensors, and supercapacitors. Out-of-plane charge carrier mobilities (µout-of-plane) across the bulk of the active material host and in-plane mobilities (µin-plane) parallel to a substrate are highly sensitive to local morphological features along their migration pathways. In general, the magnitudes of µout-of-plane and µin-plane are very different, in part because these carriers experience different morphological environments along their migration pathways. Suppressing the impact of variations in the morphological order/disorder on carrier migration remains an important challenge. While much is known about µin-plane and its optimization for devices, the current challenges are associated with µout-of-plane and its optimization for device performance. Therefore, this review is devoted to strategies for improving µout-of-plane in neat CP films and the implications for more complex systems, such as D:A blends which are relevant to OPV devices. The specific strategies discussed for improving µout-of-plane include solvent/field processing methods, chemical modification, thickness confinement, chemical additives, and different post-annealing strategies, including annealing with supercritical fluids. This review leverages the most recent fundamental understanding of mechanisms of charge transport and connections to morphology, identifying robust design strategies for targeted improvements of µout-of-plane.

Elucidating nanoscale mechanical properties of diabetic human adipose tissue using atomic force microscopy.

Obesity-related type 2 diabetes (DM) is a major public health concern. Adipose tissue metabolic dysfunction, including fibrosis, plays a central role in DM pathogenesis. Obesity is associated with changes in adipose tissue extracellular matrix (ECM), but the impact of these changes on adipose tissue mechanics and their role in metabolic disease is poorly defined. This study utilized atomic force microscopy (AFM) to quantify difference in elasticity between human DM and non-diabetic (NDM) visceral adipose tissue. The mean elastic modulus of DM adipose tissue was twice that of NDM adipose tissue (11.50 kPa vs. 4.48 kPa) to a 95% confidence level, with significant variability in elasticity of DM compared to NDM adipose tissue. Histologic and chemical measures of fibrosis revealed increased hydroxyproline content in DM adipose tissue, but no difference in Sirius Red staining between DM and NDM tissues. These findings support the hypothesis that fibrosis, evidenced by increased elastic modulus, is enhanced in DM adipose tissue, and suggest that measures of tissue mechanics may better resolve disease-specific differences in adipose tissue fibrosis compared with histologic measures. These data demonstrate the power of AFM nanoindentation to probe tissue mechanics, and delineate the impact of metabolic disease on the mechanical properties of adipose tissue.

Self-Assembled Monolayers at the Conjugated Polymer/Electrode Interface: Implications for Charge Transport and Band-Bending Behavior.

The role of self-assembled monolayers (SAMs), trichloro(1 H,1 H,2 H,2 H-perfluorooctyl) (FTS) and octadecyltrichlorosilane (OTS), deposited on indium tin oxide (ITO) substrates, on electronic properties of the poly(3-hexylthiophene) (P3HT)/SAM/ITO system is reported. SAMs, well known for modifying the surface energies of materials, are also known to modify the work functions (WFs) of semiconductors. Unsurprisingly, differences between the band-bending behaviors of P3HT/ITO, P3HT/OTS/ITO, and P3HT/FTS/ITO systems were observed because the SAMs modify the WF of ITO. However, the degrees of band bending occurring in these systems could not be attributed solely to the modified WFs of the substrate. This was apparent based on measurements of samples that included P3HT films prepared with different morphological structures. Changes in the morphological structure, due to different deposition methods and surface energies of the substrates, are necessarily connected to changes in the electronic structure, including changes in the electronic density of states (DOS), of P3HT. An association between (i) the WF differences between P3HT, ITO, and SAM/ITO substrates, (ii) the surface energies of the ITO and SAM/ITO substrates, which influence the morphology of the deposited P3HT layer, (iii) the DOS widths of P3HT, and (iv) the degree of band bending is suggested.

Local Optoelectronic Characterization of Solvent-Annealed, Lead-Free, Bismuth-Based Perovskite Films.

Traditional organolead-halide perovskite-based devices have shown rapid improvements in their power conversion efficiency in less than a decade, yet challenges remain for improving stability and film uniformity, as well as the elimination of lead to address toxicity issues. We fabricated lead-free methylammonium bismuth iodide (MBI) perovskite films and studied the effect of solvent annealing with dimethylformamide (DMF) on both (1) the crystallinity and structure of the films with X-ray diffraction and scanning electron microscopy and (2) the local optoelectronic properties of the films as measured via (photo)conductive atomic force microscopy. We found that solvent annealing leads to improved crystallinity and increased grain size in the MBI films as compared to the thermally annealed films. Furthermore, solvent-annealed MBI films show significantly increased electrical conductivity in the out-of-plane direction. Photoconductivity in both solvent-annealed and thermally annealed MBI films was increased in the grain interiors versus the grain boundaries. It was observed that DMF-induced solvent annealing impacts charge transport through the film, which can be a unique design parameter for optimizing local optoelectronic properties. By studying how solvent annealing affects the MBI film structure and changes the ways in which charges are transported through the film, we have developed a better understanding of how local optoelectronic properties are affected by DMF annealing.